Dry cleaning composition and method



Patented Feb. 3, 1942 DRY CLEANING COMPOSITION METHOD AND Lawrence H.Flett, Hamburg, N. Y., assignor to AlliedCliemical & Dye Corporation, acorporation oi. New York I No Drawing.

14 Claims.

This invention relates to improvements in dry cleaning of textile andrelated materials. It relates particularly to improved compositionsioruse in dry cleaning and to processes of dry cleaning in which saidimproved compositions are employed.

I have found, according to the present invention, that salts of aromaticsulfonic acid compounds which contain at least one alkyl group with 3 ormore carbon atoms constitute valuable ingredients for dry cleaningcompositions.

The said alkyl group or groups may be directly linked to the nucleus ofthe aromatic sulfonic acid compounds or may be joined thereto by meansof an atom or radical, as fomexample, an

oxygen atom, or one of the radicals NH-,

NHCO, CO, etc. They may be alkyl hydrocarbon radicals or may containsubstituents such as halogen, aryl, alkoxy, etc. Compounds in which theradical COOX (in which X represent hydrogen or a salt forming cation) ispresent as a substituent in the alkyl group are not included in thepresent invention in view of their inferior properties.

The aromatic nuclei of said sulfonlc acid compounds may be mononuclear,as for example phenyl, tolyl, etc., or pol'ynuclear, as for examplenaphthyl, diphenyl, etc. They may be free from further substituents orthey may contain one or more substituents, as for example, OH, alkyl,alkoxy, and/or carboxyl (in the free acid or salt form).

The said sulfonic acids correspond with the formula:

where A is a mono or polynuclear aromatic res-' idue; R is a saturatedor unsaturated substituted or unsubstituted alkyl group which containsat least three carbon atoms and in which the substituents, if any, maybe alkoxy, ar'yl, halogen, etc.; X is either a bond joining a carbonatom of the alkyl group represented by R to a carbon atom of thearomatic nucleus. or is a linking atom or group of atoms, e. 'g.,--O---, NH---, NHCO, CO, etc.; and y and z are integers, a beingpreferably 1.

This invention includes the use of various salts of the said sulfonicacids in which the hydrogen of the sulfo or other acidic groups isreplaced by,an inorganic or organic salt-forming radical. Among the moreeasily procured salts are the ammonium, alkali-metal, alkaline earthApplication September 25, 1935, Serial No. 42,164

metal salts and the salts in which the acidic groups are neutralized bythe more common or- 'ganic bases, such as mono-, di-, ortriethanolamine, pyridine, ethylene diamine, amylamines, triethylenetetramine, etc. If the salt-forming basic component is poly basic,

be of a detergent nature.

A preferred class of compounds comprises the mono-nuclear aromaticsulfonic acid compounds containing at least'one alkyl group with aminimum of 8 carbon atoms, or at least two alkyl groups containing atleast 3 but less than 8 carbon atoms. Preferably the alkyl groups aredirectly linked to the aromatic nucleus and are free from substituents,and more particularly are saturated hydrocarbon radicals; and preferablythe aromatic nucleus contains one or more hydroxyl groups assubstituents. Among the'preferred alkylated aryl sulionates with analkyl group of 8 or more carbon atoms, those with one such alkyl groupare more efiective than com- The compounds which contain an alkyl groupof 12 or more carbon atoms are moreefiective than compounds with severalalkyl groups. The .compounds which contain an alkyl groupflof lii ormore carbon atoms are more effective vthan those with the alkyl groupsof lowercarbon content.

The following arespeciflc'ariomatic' sul'ionic acid compoundsillustrative of those which may .be employed in accordance withthepresentinvention: sodium tetradecylphenonesulfonate, diisopropylnaphthalene sodium sulionate, sodium secon'dary-hexyl phenol sulfonate,sodium capryl hydroxy diphenyl sulfonate, sodium tetradecyl phenetolesulfonate, sodium tetradecyl cresol sulfonate, sodium tetradecylnaphthalene sulfonate, sodium lauryl phthalate sulfonate, sodium stearictoluidide sulfonate, and sodium para-cymene sulfonate. It will beunderstood, however, from the disclosure herein that the invention isnot limited thereto.

The said salts ofaromatic sulfonic acid compounds, and particularlytheir alkali metal and organic ammonium salts, are soluble in volatileorganic liquids of the type generally employed in dry cleaning (e. g.cleaning naphtha, carbon tetrachloride, trichlorethylene, etc.) in whichthey exert a desirable detergent action. The said salts of aromaticsulfonic acid compounds further have the valuable property of formingemulsions of water in the said organic liquids, and hence may beemployed for the production of dryit may be neutral- 'ized in part withthe above defined sulfonic acids and in part by other acidic materialswhich may cleaning compositions in the form of emulsions containing theorganic dry cleaning liquid in the external phase and water in theinternal phase.

One of the outstanding characteristics of the new dry-cleaningcompositions of this invention is their ability to achieve excellentcleaning action in low concentrations. The said dry cleaningcompositions are characterized in that the weight ratio of sulfonic acidsalt to organic, substantially water-immiscible solvent or solventmixture, is not greater than 1.0 to 100, and preferably less than 0.3 to100. Improved finish and/or feel of the cleaned fabric, e. g., silks,can often be obtained by incorporating ,a small amount of paraflln waxor similar agent in the cleaning compositions.

Further, alkyl phenol sulfonic acid compoundsv which correspond with thegeneral formula in which A represents hydrogen or a methyl group, Rrepresents a nuclear alkyl hydrocarbon radical (saturated orunsaturated) containing 12 or more (especially 14 to 19) carbon atoms,and M represents hydrogen or a metal, such as an alkali metal, or anammonium or an organic ammonium radical, constitute a preferred class ofingredients for dry cleaning compositions. Dry cleaning fluids in whichthe said .alkyl phenol sulfonic acid compounds and water are presentserve not only to remove oil soluble soil from the material to becleansed but have the additional advantage, in view of the superiordetergent action of the said alkyl phenol sulfonic acid compounds inwater, of also removing water soluble soil and spots. Inasmuch as thewater solutions of the said compounds in the form of their alkali metalsalts are neutral in reaction, dry cleaning compositions containingwater and said compounds may be safely used for the cleaning of delicatesilks and other fine fabrics.

The said alkyl phenol sulfonic acid compounds are derivatives of phenol(hydroxy benzene) and.

of the cresols (1.2-, 1.3-, and 1.4- methyl-hydroxy-benzene) in whichthe alkyl hydrocarbon radical represented by R. in the foregoing formulais directly linked to a nuclear carbon atom and in which the sulfonategroup (represented by SO3M in the foregoing formula) is also directlylinked to a nuclear carbon atom. For convenience they willbe'hereinafter referred to as "alkyl phenol sulfonates which termgenerically includes th phenol and cresol derivatives, whether in theform of the free sulfonic acids or their salts. The alkyl phenolsulfonates preferably employed in accordance with the pres ent inventionare those in which the alkyl group contains a branched carbon chain,whether linked to the benzene nucleus by an end carbon atom (an alphacarbon atom) or an intermediate carbon atom (that is, whether a primary,secondary or tertiary alkyl group).

The following examples illustrate several methods of preparing alkylphenol sulfonates useful in connection with the present invention. Itwill be evident from a consideration of the disclosure herein that theinvention is not limited to the use of products prepared in this mannerbut includes products of the type referred to herein prepared in otherways. The parts are by weight and temperatures are in degreescentigrade.

Example 1.-T- parts of commercial cetyl alcohol (containing 30 to 40 percent of normal cetyl alcohol, 30 to 40 per cent of higher alcohols thancetyl, e. g. stearyl alcohol, etc., about 10 per cent of normal laurylalcohol and about 20 per cent of normal myristyl alcohol), 100 parts ofphenol, and 100 parts of anhydrous zinc chloride are heated at to 180,under a reflux condenser, with agitation for 16 hours. The condensationproduct is washed with water until practically free from water solubleproducts. The resulting oil is fractionally distilled in vacuo. Thefraction of the. distillate which is collected between 195 and 240 at 15mm. pressure of mercury is a faint yellow to water-white oil consistingchiefly of a mixture of alkyl phenols having the probable generalformula:

in which Rm is a straight chain hydrocarbon radical having the formula:

C10H21, C12H2s, C14H29 or CisHas the compound in which Rm is C14H29being a predominating compound, with a small amount of normal alkylphenols and probably some ortho isomers present.

100 parts of the resulting purified alkyl phenol mixture, 40 parts ofacetic anhydride and 106 parts of sulfuric acid mono-hydrate are mixedtogether and warmed gently to 70 to 75 until the product is completelysoluble in water and a neutral 0.2 per cent solution does not recipitatecalcium salts from a calicum chloride or other soluble calcium saltsolution containing the equivalent of 0.224 gram calcium oxide perliter. The mass is diluted with water to a final volume of 450 to 600parts and neutralized with alkali, as for example, caustic soda orcaustic potash or their equivalents. The neutral solution is clarified,if desired, by filtration, and evaporated to dryness. The product is abrown to white solid, soluble in water to give brown to water-whitesolutions. It comprises a mixture of inorganic salts (e. g. sodiumsulfate), with sulfonates of the said alkyl phenols (e. g., in the formof the sodium salts), of which mixture the inorganic salts constitute inthe neighborhood of 60 per cent. The alkyl phenol sulfonates present aresoluble in alcohol, benzene and other organic solvents.

Example 2.-A mixture of 185 parts of lauryl chloride (prepared fromcommercial lauryl alcohol), 100 parts of phenol and 30 parts of zincchloride (as a condensing agent) are heated with agitation at atemperature of to under a reflux condenser for 20 hours. The reactionmixture is allowed to.cool and the resulting oil which separates isdecanted oil and fractionally distilled in a vacuum. The fraction of thedistillate boiling between 150 and 230 at 4 mm. pressure of mercury isseparately collected. It consists chiefly of lauryl phenol.

To 20 parts of the lauryl phenol thus obtained, there is slowly added,with agitation, 20 parts of sulfuric acid mono-hydrate, and the mixtureis maintained at a temperature of 30 to 35 for 3 hours, or until thedesired sulfonati on is effected. The mass is then diluted with 400parts of water, and the solution thus obtained is neutralized atapproximately 250 SOsNa Example 3.700 parts of an olefine with a boilingpoint ranging from 237 to 262 and having an average carbon content of 14to 15 carbon atoms (and obtained by dechlorination of the monochlorhydrocarbons separated by fractionation from the products resulting fromchlorination of petroleum distillates which boil at atmosphericpressure), 700 parts of phenol, and 350 parts of anhydrous zinc chlorideare mixed and heated together while agitated under a reflux condenser ata temperature around 180 to 190 for from to 16 hours. The condensed massis diluted and washed with water until reasonably free of water-solubleimpurities,. and the crude brownish oil is distilled in vacuo. Thefraction of the distillate boiling between 195 and 240 at mm. pressureis collected separately. It is a faintly .colored to water-white oil,insoluble in water and dilute caustic soda.

100 parts by weight of the resulting 011 are mixed with 148 parts byweight of sulfuric acid monohydrate at then heated to '70-75 and heldthere until a sample is completely soluble in water and in neutral, acidor alkaline aqueous solutions, and a neutral 0.2 per cent solution doesnot precipitate calcium salts from a soluble calcium salt solutioncontaining the equivalent of 0.224 gram calcium oxide per liter. Thesulfonation mix is poured into water, diluted to a final volume of 450to 600 parts, and made neutral (for example, to delta paper, Congo redpaper, brilliant yellow, or brom-phenol-blue) with alkali, for examplecaustic soda, or potash or their equivalents. The neutral solution isevaporated to dryness. If desired, the neutral solution can be clarifiedby filtration before being evaporated to dryness. V

The product thus obtained is a mixture of which the chief components arealkyl phenol sulfonates having the probable formula (SOr-NDp R. where R0represents an aliphatic hydrocarbon group, M represents an alkali metalor equivalent derived from the base used for neutralization, and p is 1or 2 but mainly'l. For the most part, the alkyl phenol sulfonatescontain branched carbon chains in the groups represented by Re and thesegroups are connected to the phenol nucleus by primary, secondary ortertiary carbon atoms. The chief components of the mixture contain 14 or15. carbon atoms in the alkyl group represented by R42.

In the form of the alkali metal and alkaline earth metal salts it is afaintly colored light brown to white, friable solid, readily reduced toproduced by such processes as in alcohol and other organic solvents.

a comminuted or powdery form (resembling powdered soap) and readilysoluble in water. The products of the above examples contai inorganicsalts (e. g., alkali metal sulfates) in admixture with the alkyl phenolsulfonates. When it is desired to employ the alkyl phenol sulfonates ina form free from inorganic salts, they may be obtained from the mixedproducts are given in the above specific examples by taking advantage ofthe solubility of the alkyl phenol sulfonate salts Thus a mixture of asalt of the sulfonated product and an inorganic sulfate may be extractedwith alcohol, and the resulting extract may be evaporated to leave aresidue of the purified salt of the sulfonated product, as illustratedby the following specific example.

Example 4.--The neutralized solutions containing alkyl phenol sulfonatesprepared in Examples 1, 2 and 3, or equivalent aqueous solutionsprepared from the final dry sulfonates, are diluted with an equal volumeof commercial denatured alcohol, thoroughly mixed for several hours,filtered and evaporated to dryness; or the dry sulfonates are extractedwith successive portions of denatured alcohol, the total amount ofalcohol used for this'ext'raction being preferably not more thanapproximately four times the weight of thedry unextracted sulfonate, thecombined extracts are mixed and digested with a small amount of animalcharcoal, filtered and evaporated to dryness. The residue obtained ineither case is an alkyl phenol sulfonate in the salt (e. g., sodiumsalt) form, practically free from salts of mineral acids.

The following examples illustrate the use of the products hereinbeforedescribed. It will be understood, however, that these examples aremerely illustrative and that any of the other 'sulfonated productsherein described may be similarly employed. The parts are by weight.

Example 5.-Botany worsted cloth (carbonized) is soiled by immersion in acarbon tetrachloride solution of tallow, and mineral oil containing lampblack in suspension, and the soiled cloth is dried. The resulting soiledcloth shows a brightness (whiteness) of 14.3 per cent by photometrictest (Zeiss-Pulfrich photometer). 0.3 gram of the sodium lauryl phenolsulfonate prod uct of Example 2, containing about 0.15 gram of sodiumlauryl phenol sulfonate and about 0.15 gram of inorganic salts (sodiumsulfate) is mixed with cc. of cleaners naphtha. A 5 gram sample (6.3inches square) of the above soiled Botany worsted cloth is placed in apint jar containing the resulting solution together with 50 grams ofglass beads of 3 mm. diameter and agitated at 50 for 30 minutes in alaunderometer. The sample of cloth is then passed through a wringer anddried. The dried sample shows a brightness (whiteness) of. 24 per centby photometric test (Zeiss-Pulfrich photometer). When a like sample ofthe soiled cloth is similarly cleaned in the absence of the laurylphenol sulfonate, it shows a brightness (whiteness) .of 12.9 per cent;that is, the resulting sample appears more soiled than before cleaning.

Example 6.-0.25 gram of water is added to the cleansing mixture in aboveExample 5, and the resulting mixture is employed as in said example. Thebrightness (whiteness) of the cleaned sample is 30.3 per cent.

Example 7 .Trichlorethylene is substituted for the cleaners naphthaemployed in Examples 5 and 6. The procedure is otherwise the same. Thebrightness (whiteness) of the cleaned sample without the water beingpresent is 28.9 per cent and with the water present is 30.7 per cent.

Example 8.Carbon tetrachloride is substituted'for the cleaners naphthaemployed in Examples 5 and 6. The procedure is otherwise the same. Thebrightness (whiteness) of the cleaned sample without the water beingpresent is 27.7 per cent and with the water present is 29.2 per cent.

Example 9.A soiled Botany worsted cloth having a brightness (whiteness)of 9.4 per cent is prepared in accordance with theprocedure employed inExample 5. 0.15 gram oithe purified sodium cetyl phenol sulfonateobtained in accordancewith the procedure of Example 4 is employed forthe cleaning of a 5 gram sample of this soiled cloth by the procedure ofExample 5, with the exception that the cleanedsample is allowed to drywithout being passed through a wringer. The brightness (whiteness) ofthe cleaned sample is 16.6 per cent. By carrying out the procedure ofthis example in the absence of the sodium cetyl phenol sulfonate, acleaned sample is obtained having a brightness (whiteness) of 7.! percent.

It will be realized by those skilled in the art that changes may be madein the compositions, and in the processes of preparing and using them,hereinbefore described, without departing from the scope of theinvention.

The alkyl phenol sulfonates employed in accordance with the presentinvention may be prepared in various ways. According to one method ofpreparation, an alkyl phenol or cresol of the type (in which the symbolsA and R have the meaning defined above) may be treated with a sul-vfonating agent, in the presence or absence of a solvent or diluentand/or a sulfonation assistant. As sulfonating agents there may beemployed sulfuric acids of various strengths (e. g., 66 B. sulfuricacid, sulfuric acid monohydrate, oleum) chlorsulfonic acid, etc. Assolvents or diluent there may be employed any inert organic liquid whichis not readily sulfonated, such as halogenated hydrocarbons of thealiphatic and aromatic series, as for example, carbon tetrachloride,dichlorethane, tetrachlorethane, dichlorbenzene, etc. As sulfonationassistants there may be employed the lower organic acids and/or theiranhydrides, as for example, acetic acid, acetic anhydride, etc.

The sulfonation may be carried out with the aid of heating or cooling,as required, depending upon the ease of sulfonation of the alkyl phenolor cresol and the sulfonating power of the sulfonating agents. Thesulfonation of the alkyl phenol or cresol may be carried out to anextent such that mainly one, or more or less than one, sulfonic acidgroup is present in the final product (based on the alkyl phenol orcresol). In general the extent of sulfonation of the alkyl phenol orcresol treated is such as to form chiefly the mono-sulfonic acid of thealkyl phenol, and to sulfonate impurities as well, if present.

The alkyl phenol sulfonates may be employed in accordance with thepresent invention in the form of their free sulfonic acids or in theform of salts of metals (as for example, of the alkali metals) or oforganic bases, or of ammonia, etc. The salts may be obtained in anysuitable manner; for example by reacting the sulfonated product, eitherin the crude form resulting from the sulfonation or in a purified form,with a metal oxide or hydroxide, ammonia or an organic base, or of asuitable salt oi. one of these. in an amount adapted to form a neutralproduct. Among the bases. oxides and salts which may be combined withthe sulfonated products to produce salts useful in accordance with thepresent invention are, for example, sodium, potassium and ammoniumhydroxides; sodium, potassium and ammonium carbonates and bicarbonates;ammonia, magnesium oxide; ethylamine; pyridine; triethanolamine;propanolamines; butanolarnines; diamino propanol; ethylenediamine;triethylene tetramine; etc.

The sulfonated alkyl phenol products in the form of metallic salts orsalts of inorganic bases are usually yellowish to'white, friable solids;and in the form of salts of organic bases vary from viscous oils tosemi-solids to solids. In general, the salts are readily soluble inwater and in aqueous (neutral, acid or alkaline) solutions to formsolutions which are faintly colored brown oryellow, which are of a soapynature and which foam readily. In general, they are less soluble in thedry cleaning solvents than in water but they are sumciently soluble togive solutions which are adequate for use for the dry cleaning offabrics, yarns, etc. Certain of the salts, such as the salts of thearomatic monoamines and the aliphatic and aromatic polyamines, are oilswhich generally are insoluble in water, probably due in part to thepresence of small amounts of organic impurities, but soluble in organicsolvents (as for example, benzene, gasoline, etc.) and in aqueoussolutions of alkalis (presumably by conversion to the salts of thealkalis) It is to be understood that the invention includes the use ofproducts containing a plurality of alkyl phenol sulfonic acid nucleilinked together through the sulfonic acid groups by a polyvalent metalor organic basic radical, as well as products in which analkyl phenolsulfonic acid is linked through the sulfonic acid group to a diflerentacid compound by a polyvalent metal or organic basic radical.

Thus the invention comprehends compounds of the type (X) a-Z-(X'). and(x)-Z(Y)., wherein X and x' each represent the radical R Borwhich may bethe same or different, Z represents a polyvalent metal or organic base,Y represents a radical containing an acid group, n represents a wholenumber, and A and R have the meaning defined above. Examples of suchtypes of compounds are wherein X and R have the meaning defined above,and W represents a radical containing an linked by an oxygen atom to thearomatic nu-' cleus, may be rearranged to the alkyl phenol; or the alkylgroup may be substituted in the aromatic nucleus in the form of a ketoneby condensing phenol or a cresol with a fatty 'acid or acid chloridecorresponding with the desired alkyl group, in place of an alkylatingagent in the process just, enumerated, and subsequently reducing theresulting ketone.

In the condensation of phenol or a cresol with an alkylating agent theremay be employed as alkylating agents non-aromatic alcohols (as forexample, straight-chain, primary monohydric alcohols; straight-chain,secondary monohydric alcohols; branched-chain primary alcohols;branched-chain secondary alcohols; tertiary alcohols of all types;etc.), olefine hydrocarbons containing straightor branched-chains, andcontaining a double bond preferably between the ultimate and penultimatecarbon atoms; and halogen derivatives of hydrocarbons; all containing atleast 12 carbon atoms and preferably 12 to 23 carbon atoms in an alkylhydrocarbon chain. A preferred alkylating agent is commercial laurylalcohol containing a mixture of normal alcohols, including a majorproportion of lauryl alcohol together with cetyl alcohol, myristylalcohol, etc. As condensing agents there may be employed anhydrous zincchloride, anhydrous aluminum chloride, anhydrous antimonic chloride,anhydrous ferric chloride, zinc, copper, etc.

It is to be noted that mixtures of two or more of the sulfonatedproducts hereinbefore referred to may be employed.

For the purpose of illustration, the following additional products, inthe form of the free sulfonic acids and in the salt (e. g., sodium salt)form, are mentioned as suitable for use in accordance with the presentinvention; but the invention is not limited thereto, as will be evidentfrom the disclosure herein:

Cetyl phenol sulfonate (resulting from the condensation of cetyl alcoholwith phenol and sulfonation of the resulting cetyl phenol) Alkyl metaorpara-cresol sulfonates, or mixtures thereof, in which the alkyl groupscorrespond with the alcohols contained in commercial cetyl alcohol (andobtainable by condensing commercial cetyl alcohol with ortho-, metaorparacresol and sulfonating the resulting mixture of alkyl ortho-, metaorpara-cresols);

Lauryl cresol sulfonates, 'or mixtures thereof with homologous alkylphenol or cresol sulfonates (obtained by condensing cresol with acommercial mixture of lauryl alcohol and homologous fatty alcoholscorresponding with the fatty acids of cocoanut oil, and sulfonating theresulting alkyl phenol or alkyl cresol mixture);

Octadecyl (stearyD- phenol sulfonate (l-methyl-heptadecyl phenolsulfonate) Normal primary hexadecyl phenol sulfonate (obtainable byreducing palmito- (hydroxy) benzophenone and sulfonating the resultingalkyl phenol) Pentadecyl phenol sulfonate (obtainable by condensingphenol with the pentadecyl alcohol resulting from the polymerization ofamyl alcohol, and sulfonating the resulting alkyl phenol) Tricosylphenol sulfonate (obtainable by condensing tricosanol-7 with phenol,followed by sulfonation);

Alpha-alpha-dimethyl-hexadecyl-phenol sulfonate (obtainable bycondensing dimethyl pentadecyl carbinol with phenol and sulfonating theresulting alkyl phenol).

This application is a continuation-impart of my application Serial No.691,082, filed September, 26, 1933.

I claim:

1. A dry cleaning composition comprising a solution in an organic liquidof the dry cleaning type of a salt of an aromatic sulfonic acid compoundcontaining at least one alkyl group with at least 3 carbon atoms, andcorresponding in the free acid form with the formula gen, X is a bondjoining a carbon atom of the alkyl group R to a carbon atom of thearomatic nucleus A or is a linking atom or radical, and y and z areintegers.

2. A dry cleaning composition comprising a solution in an organic liquidof the dry cleaning type of a salt of an aromatic sulfonic acid compoundcontaining at least one alkyl hydrocarbon group with at least 8 carbonatoms.

3. A dry cleaning composition comprising an organic liquid of the drycleaning type and a small amount of a dry cleaning assistant comprisingan alkyl phenol sulfonate in which the alkyl radical consists of analkyl hydrocarbon radical containing at least 12 carbon atoms.

4. A dry cleaning composition comprising an emulsion of water in avolatile organic liquid of the dry cleaning type, the water being in theinternal phase, and a salt of an aromatic sulfonic acid compoundcontaining at least 1 alkyl hydrocarbon group with at least 3 carbonatoms as an emulsifying agent for the water and as a dry cleaningassistant, said salt being selected from the group consisting of alkalimetal, alkali earth metal, ammonium and organic ammonium salts.

5. A dry cleaning composition comprising an emulsion of water in avolatile organic liquid of the dry cleaning type, the water being in theinternal phase, and a salt of an aromatic sulfonic acid compoundcontaining at least 1 open chain alkyl hydrocarbon group with at least12 carbon atoms as an emulsifying agent for the water and as a drycleaning assistant, said salt being selected from the group consistingof alkali metal, alkali earth metal, ammonium and organic ammoniumsalts.

6. A dry cleaning composition comprising an emulsion of water ina.volatile organic liquid of the dry cleaning type, the water being inthe internal phase and an alkyl phenol sulfonate in which the alkylradical consists of. an alkyl hydrocarbon radical containing at least 12carbon atoms as an emulsifying agent for the water and as a dry cleaningassistant.

7. A dry cleaning composition comprising an emulsion of water in avolatile organic liquid of the dry cleaning type, the water being in theinternal phase, and a salt of an aromatic sulionic acid compound solublein said mixture and containing at least 1 open chain alkyl hydrocarbongroup with at least 12 carbon atoms as an emulsifying agent for thewater and as a dry cleaning assistant.

8. A dry cleaning composition comprising an emulsion of water in avolatile organic liquid of the dry cleaning type, the water being in theinternal phase, and a salt of a mononuclear aromatic sulfonic acidcontaining an alkyl hydrocarbon group with at least 12 carbon atomsdirectly linked to the aromatic nucleus as an emulsifying agent for thewater and as a dry cleaning assistant, said salt being selected from thegroup consisting of alkali metal, alkali earth metal, ammonium andorganic ammonium salts.

9. A dry cleaning composition comprising a volatile organic liquid ofthe dry cleaning type and not more than 1 per cent of the weight of theorganic liquid of a soluble salt of an aromatic sulfonic acid compoundcontaining at least one alkyl group with at least 8 carbon atoms, andcorresponding with the formula wherein A is an aromatic residue,R is analkyl group containing at least 8 carbon atoms, and which may besubstituted by alkoxy, aryl or halogen, X is a bond joining a carbonatom of the alkyl group R to a carbon atom of the aromatic nucleus A oris a linking atom or radical, M is an alkali metal or an alkali earthmetal or an am- -monium or organic ammonium radical, and y 11. A drycleaning composition comprising a solution in a voltatile organic liquidof the dry cleaning type or a salt of a mononuclear aromatic sulionicacid containing an alkyl hydrocarbon group with at least 12 carbon atomsdirectly linked to the aromatic nucleus.

12. A dry cleaning composition comprising a volatile organic liquid ofthe dry cleaningtype and a dry cleaning assistant which is a salt of amononuclear aromatic suli'onic acid containing an alkyl hydrocarbongroup with at least 12 carbon atoms directly linked to the aromaticnucleus in an amount not exceeding 1 per cent by weight or said liquid,said salt being selected from the group consisting of alkali metal,alkali eglrth metal, ammonium and organic ammonium s ts.

13. A dry cleaning composition comprising an emulsion of water in avolatile organic liquid of the dry cleaning type, the water being in theinternal phase, and a salt of a mononuclear aromatic suli'onic acidsoluble in said mixture and containing an alkyl hydrocarbon group withat least 12 carbon atoms as an emulsifying agent for the water and as adry cleaning assistant.

14. A dry cleaning composition comprising an emulsion of water in avolatile organic liquid of the dry cleaning type, the water being in theinternal phase, and a salt of an aromatic sulfonic acid compoundcontaining at least one alkyl group with at least 3 carbon atoms, andcorresponding inthe free acid form with the formula as an emulsifyingagent for the water and as a dry cleaning assistant, wherein A is anaromatic residue, R is an alkyl group containing at least3 carbon atomsand which may be substituted by alkoxy, aryl or halogen, X is a bondjoining a carbon atom of the alkyl group R to a carbon atom of thearomatic nucleus A or is a linking atom or radical, and 11 and z areintegers.

LAWRENCE H. FLETT.

